Rare Earth Element Enrichment Research Articles

Scalable and facile fabrication of sulfonic-acid-functionalized porous hypercrosslinked polymers for efficient recovery of rare earth elements from tailing wastewater

The separation and enrichment of rare earth elements (REEs) from tailing wastewater is of great significance for the sustainable supply of REEs and environmental remediation. As Al3+ exhibits extreme similar properties with REE3+, selective recovery of REE3+ from the sulphate tailing wastewater remains a considerable challenge. Based on the difference in the binding stability of REE3+ and Al3+ with sulfate ions, the utilization of sulfonic acid groups may provide a promising method for enhancing the selectivity of REE3+/Al3+ in the sulphate aqueous solution. Herein, a series of sulfonic-acid-functionalized hyper-crosslinked polymers (SHCP-Ps) were successfully synthesized through a facile, scalable and one-step method catalyzed by chlorosulfonic acid, which has the advantages of high sulfonic acid density (3.27 mmol/g), specific surface area (1044.6 m2/g), abundant micropores and superhydrophilicity. These properties result in SHCP-P exhibiting fast adsorption kinetics (30 min) and high adsorption capacities (106.78 mg/g (La), 111.99 mg/g (Eu) and 126.27 mg/g (Lu)). Additionally, it exhibits extremely high REE3+/Al3+ selectivity (SF(La/Al) = 6929, SF(Eu/Al) = 4810, SF(Lu/Al) = 3003) in sulfate medium, surpassing that of most existing REEs adsorbents. Upon application of SHCP-P to actual wastewater, the recovery rate of total REE3+ was observed to reach 87 %, while the adsorption rate of Al3+ was found to be 0. Simultaneously, SHCP-P exhibits both high reusability and magnification synthesis capabilities. The results indicate that SHCP-P has significant potential for industrial applications in the selective recovery of REEs from tailing wastewater.

Mesoproterozoic depleted spinel peridotites metasomatized by high-K hydrous melt in the Patagonian back-arc

Here we report the first investigation of spinel-bearing mantle xenoliths from Los Gemelos volcano, Canquel Plateau, Patagonia. They are highly-depleted Mesoproterozoic (ReOs model ages of 1.3–0.9 Ga) harzburgites and clinopyroxene-poor lherzolites characterized by typical indicators of partial melt extraction, such as low whole-rock Al2O3 and CaO contents (<1.5 wt%), high Mg# of silicate phases (90–95), and Cr-rich spinel (Cr# 0.20–0.42). Depletion of incompatible highly siderophile elements (Re, Ru, Pd) relative to the primitive upper mantle supports high degrees of melt extraction. The occurrence of phlogopite and K-rich alkaline glass veins with high- and low-SiO2 compositions is clear evidence of modal metasomatism. The light rare earth element (LREE) enrichment in clinopyroxene, as well as the whole-rock U-shaped REE pattern, confirms cryptic metasomatism. This melt-rock interaction is corroborated by major (i.e., Mg# vs. basaltic elements) and trace (i.e., La/YbN vs. Sr/Y and Ti/Eu; and Sr vs. Ti/Eu) element contents of pyroxenes. The calculated compositions of melts in equilibrium with clinopyroxene coexisting with phlogopite suggest interaction with slab-derived materials. This metasomatism has been generated by a chromatographic fractionation-reaction process, from deep to shallow mantle domains. The percolation of a high-K hydrous magma probably is associated with the upwelling of asthenospheric material through a slab-window, which caused partial melting of oceanic crust and overlying sediments during the Paleocene. The varying intensities of metasomatic imprints recorded by mantle xenoliths from Los Gemelos provide valuable insights into the interaction of slab-derived materials near the lithosphere-asthenosphere boundary, at a distance of ∼600 km from the Andean volcanic arc.

Mobility and fractionation of rare earth elements during black shale weathering: Implications from acid rock drainage and sequential extraction study

Black shale is a type of sedimentary rocks that are enriched in rare earth elements (REEs). It is of both economic importance and environmental significance to understand REE mobility during black shale weathering. The present study approaches to this by analysing REEs in acid rock drainage (ARD) from black shale weathering system, fresh and weathered black shales, soils derived from black shales, and sequential extractants from black shales at Dongping town in Hunan province (China). Results showed that REEs had variable high concentrations in ARD as shown by total REE + Y (∑REY) concentrations from 162 to 4074 (μg/L). REEs in ARD displayed hat-shape NASC-normalized patterns with significant enrichments of middle REEs (MREE) relative to light REEs (LREE) and heavy REEs (HREE), and had significant negative Ce (Ce/Ce⁎ = 0.6) and positive Y (Y/Y⁎ = 1.5) anomalies. MREE enrichment in ARD could be evaluated using MREE/MREE⁎ values, which varied from 1.43 to 1.81 with a mean of 1.65, distinctly higher than those of whole rocks (around 1.0). 1 M HCl extraction results suggested that REEs were integratedly mobilized during shale weathering, while six-step extraction studies identified that REEs in ARD resulted from exchangeable and Fe-oxide fractions with MREE and HREE enrichment in shales respectively. MREE in exchangeable and HREE in Fe-oxide fractions were preferentially released during weathering, as illustrated by plots of MREE/MREE⁎ against HREE/LREE ratios of ARD and six-step extractants. Therefore, geochemical processes for REE mobility during black shale weathering included integrated mobilization and preferential release. Integrated REE mobilization resulted from the dissolution of REE-bearing minerals and oxidation of sulfides. Preferential REE release resulted from acid fluids produced by sulfide oxidation during weathering. Thus, a new model was proposed for interpreting geochemical processes of REE mobility during black shale weathering, and for understanding REE distribution in ARD from natural and anthropogenic systems.

Enhanced enrichment of rare earth elements during pedogenesis under subtropical climate

Rare earth elements (REE) are crucial strategic resources, and weathering-crust rare earth deposits are one of the primary sources. To systematically understand the geochemical behavior (e.g., enrichment and leaching) of REE in soils (or weathering crusts) formed from diverse parent rocks under varying climatic conditions, 171 soil profiles (weathering crusts) developed from three main types of parent rocks (granite, basalt, and carbonate rock) worldwide were studied. Granite shows the highest concentration of rare earth elements at 264 (interquartile range (IQR): 278) ppm, 171 (IQR: 151) ppm and 11.9 (IQR: 36.4) ppm in basalt and carbonate rock, respectively (median test: p &lt; 0.05). The median REE values within the soil profiles were significantly different (median test: p &lt; 0.05), with the concentration of 318 (IQR: 441) ppm, 267 (IQR: 217) ppm and 207 (IQR: 417) ppm in soils derived from granite, carbonate rock, and basalt, respectively. Principal component analysis (PCA) and Linear mixed-effects models (LME) revealed that soils developed from granite and basalt inherit the mineral characteristics of their parent rocks, with REE concentrations primarily influenced by the REE content of the parent rock and climate. In contrast, the REE concentrations in soils developed from carbonate rocks are predominantly controlled by climate. LME and correlation analysis indicates that the enrichment of REE (Q REE ) shows a trend of initially increasing and then decreasing with rising temperature and precipitation, due to variations host clay minerals. The greatest enrichment occurs in the subtropical region (mean annual temperature (MAT) = 15 ̶ 23 °C; mean annual precipitation (MAP) = 1000 ̶ 2000 mm); weathering-crust type REE deposits are primarily found in the subtropics.

Enhanced deep-water circulation facilitated rare earth elements enrichment in pelagic sediments from the northwestern Pacific Ocean

The lack of knowledge about the enrichment mechanism of rare earth elements and yttrium (REY) in deep-sea sediments is impeding the development of theories and exploration strategies for pelagic REY-rich sediments. Ocean circulation variability seems to be crucial in enriching REY in pelagic sediments, which, however, has not been extensively studied. Here, we examined the Pb-Nd isotopic signals of bottom water recorded by the authigenic ferromanganese oxyhydroxide fractions, as well as the Mn/Al and Mn/Ti ratios of bulk samples from a well-dated sediment core in the northwestern Pacific Ocean. These proxies consistently indicate that enhanced deep-water circulation occurred in the study area at ∼11.5–9.5 Ma, which was most likely to be caused by changes in the flow path of bottom currents. The age of this distinct event consists with the forming age of highly REY-rich sediments. We propose that enhanced deep-water circulation in seamount areas could increase the flux of micronodules and fish debris into the pelagic sediments, facilitating the scavenging of REY from seawater. Our findings establish a connection between enhanced deep-water circulation and the enrichment of REY in pelagic sediments.

Recycling of terrigenous sediments recorded in late Permian-early Triassic Fe-rich intrusions from Yunkai Massif, South China

The origin of Fe-rich intrusion remains debatable regarding the respective role of magmatic evolution and Fe enrichment in the source. Here, we report detailed mineral and bulk-rock geochemistry of Permian-Triassic (251–250 Ma) mafic intrusions from the Tengxian area in Yunkai Massif, South China. These rocks consist of hornblende norites, show Fe-rich affinities with high FeO*(FeO* = FeOt / (FeOt + MgO) in weight ratio, >0.8, based on total iron oxide in the rock), and exhibit significant enrichment in large ion lithophile elements (LILEs) and light rare earth elements (LREEs) but depletion in Sr and high field strength elements (HFSEs), resembling subduction-related magmas. In addition, they show remarkable features that include very high δ18O values in zircon (δ18O = 8.8–10.6 ‰) and apatite (δ18O = 8.7–10.8 ‰), and extremely enriched SrPb [e.g. 87Sr/86Sr(i) = 0.7181–0.7196, 207Pb/204Pb(i) = 15.77–15.78, 208Pb/204Pb(i) = 38.95–39.05] and nonradiogenic NdHf isotopic compositions [e.g. εNd(t) = −11.1 ~ − 10.1, εHf(t) = −8.8 ~ −7.3] in bulk rocks. These characteristics distinguish the Tengxian norites from modern arc basalts and subduction-related magmas in the Paleo-Pacific Tectonic Domain. Instead, they are isotopically similar to Cenozoic Tibetan and Mediterranean potassic to ultrapotassic rocks in the Tethys Tectonic Domain. Regardless of variable influence by orthopyroxene and plagioclase accumulation, the intrinsically low SiO2 and high FeOt and Fe/Mn ratios in these rocks were likely attributed to significant contribution of a Fe-rich mantle component such as Si-poor pyroxenite, which might have formed through crystal accumulation of mafic magmas at mantle conditions. The highly evolved Sr-Nd-Pb-Hf isotopic signatures and very high δ18O values in zircon and apatite required substantial (10–20 %) involvement of recycled crust in the mantle source. The combined mineral and bulk-rock geochemical data suggest that the parental magmas for the Tengxian norites originated from a metasomatized mantle wedge through addition of terrigenous sediment-derived melt following the subduction of Paleo-Tethys Ocean beneath the Yunkai Massif.

Surface complexation of rare earth elements on goethite in sea-floor hydrothermal environment: Insight from first principles simulations

Deep-sea mud shows tremendous resource potential for rare earth elements (REEs) and its formation is closely associated with sea-floor hydrothermal activities. Iron (oxyhydr)oxides link the sources and sinks of REEs in sea-floor hydrothermal systems. However, the complexation mechanisms of REEs on iron (oxyhydr)oxides have not been well understood yet. In this study, by using the first principles molecular dynamics technique, we first calculated the pKa’s of surface groups on goethite (110) surface at elevated temperatures relevant to sea-floor hydrothermal systems and then evaluated the complexation structures and free energies of REEs on goethite (110) and (010) surfaces using the method of constraint by taking Sc3+, Y3+, and La3+ as model REE cations. The results show that REE complexation occurs in mildly acidic to neutral conditions. The most thermodynamically stable complexes of REEs are bidentate complexes on two neighboring FeOH sites on goethite (110) surface and tridentate complexes on two neighboring FeOH sites plus one Fe2OH site on goethite (010) surface. Sc3+ complexes match the goethite lattice and can be incorporated into the lattice. The stabilities of REE complexes increase with the distance from hydrothermal vents. Complexation of Y3+ is less favored on goethite compared to other REEs whereas Sc3+ prefers complexation on goethite (010) surface and La3+ exhibits similar stabilities on both (010) and (110) surfaces. The derived atomic level complexation mechanisms would be helpful for the interpretation of experimental data and the prediction of REEs’ behavior in the sea-floor. The findings presented here provide valuable insights into REEs fractionation and enrichment in deep-sea muds.

Ages and geochemistry of garnet reveal multi-types of iron-copper mineralization in the Eastern Tianshan, NW China

The Aqishan-Yamansu Fe-Cu-Au metallogenic belt in the Eastern Tianshan, NW China, hosts numerous Fe and Fe-Cu deposits that may have different genetic models, such as volcanic-hosted and skarn/IOCG types. These variations in genetic models are attributed to whether the mineralization is associated with hydrothermal activity related to volcanic or intrusive rocks. This study primarily focuses on garnets formed during the early skarn alteration in the Shuanglong Fe-Cu and Shaquanzi Fe deposits within this belt. Garnets from the Shuanglong deposit can be divided into two types and exhibit general homogeneity, with SL-Grt1 being Fe-rich and subsequently replaced by the Fe-poor SL-Grt2. Garnets from the Shaquanzi deposit display complex zonation patterns, SQZ-Grt1 show core–oscillatory zoned rim and SQZ-Grt2 show core–mantle–oscillatory zoned rim. Laser-ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) dating of SL-Grt1 and SL-Grt2 produced lower intercept 206Pb/238U ages ranging from 318.0 ± 6.4 Ma to 303.7 ± 16.4 Ma, coinciding with the multi-stage granite occurrence. In contrast, SQZ-Grt1 and SQZ-Grt2 yielded ages between 328.0 ± 2.6 Ma and 320.4 ± 1.7 Ma, corresponding to the timing of the hosted rhyolite. SL-Grt1 show light rare earth element (LREE) enrichment, and low concentrations of high field strength elements (HFSE), such as V and Zr, and appears to have formed rapidly within an open system. Conversely, SL-Grt2 is characterized by heavy rare earth element (HREE) enrichment and elevated HFSE contents, which could be formed slowly in a closed system. The variable composition in the SQZ-Grt1 and SQZ-Grt2 record cyclical changes in fluid kinetics (vigorous fluid flow vs. fluid stagnation). The cyclical zones in SQZ-Grt2 with HREE and HFSE concentrations below the detection limit indicate multiple inputs of external seawater. The distinct characteristics between Shuanglong and Shaquanzi garnets may reflect the difference between the single magma intrusion and complex volcanic activity. Combining previously published chronological data, this study elucidates a transition from the Middle Carboniferous volcanic-hosted Fe deposits (335–320 Ma) to the Late Carboniferous intrusion-related skarn or IOCG type Fe-Cu deposits (310–300 Ma) in the Aqishan-Yamansu belt.

Synchronous felsic volcanism and carbonate sedimentation as a setting for VMS deposits localization at the Salair terrane, NE Central Asian Orogenic Belt

The Salair terrane located in the northern part of the Central Asian Orogenic Belt (CAOB) contains many epithermal deposits including volcanogenic massive sulphide (VMS) deposits. The host rocks mainly consist of felsic volcanic rocks such as lavas, volcanic breccias and tuffs that associated with thick strata of carbonates. In this study, we present zircon U–Pb ages, whole rock geochemistry, and Nd isotope data from the volcanic rocks, and results of geochemical and isotope (Sr, C, O) studies of carbonates to constrain their age and petrogenesis, and to characterize the tectonic setting. Zircon U–Pb dating reveals that the ore-bearing felsic lavas have age of 519.3 ± 1.9 Ma, while the felsic tuffs have age of 516.0 ± 0.9 Ma. These volcanic rocks are characterized by high SiO2 and Na2O contents, enrichment in light rare-earth elements, remarkable negative Eu anomalies, and pronounced depletion in Nb, Ta, P, and Ti. They have depleted ɛNd(t) values ranging from +4.9 to +6.3, and young two-stage Nd model ages (from 0.82 to 0.64 Ga). The felsic volcanic rocks from the Salair terrane are interpreted as highly evolved I-type magmatic rocks that might be produced by high degree partial melting of juvenile lower crust without a significant contribution of ancient crust and without crustal reworking.Felsic volcanism was accompanied by the formation of thick strata of carbonates. These carbonates are marine limestones with Mg/Ca ratios less than 0.007, δ18O(SMOW) values from 17.1 to 23.8 ‰ and δ13C(PDB) values between –0.9 and +0.9. Their Sr isotope composition varies in a narrow range within 0.70844–0.70859 that interpreted as representing proxy for coeval seawater. These values are consistent with depositional ages of 520–510 Ma and confirms the synchronicity of the formation of carbonates and felsic volcanism. Based on the regional geology and geochemistry, the ore-host rocks of the Salair terrane were formed in the back-arc setting where the marine transgression occurred as a result of graben subsidence. It is important for better understanding epithermal deposits in the northern CAOB and might provide new insights about prospecting the VMS deposits in similar tectonic settings.

1.38 Ga magmatism and the extension tectonics in East Kunlun, northern Tibetan Plateau

Numerous Paleo- to Mesoproterozoic magmatic rocks were emplaced during the assembly, accretion and break-up of the Columbia supercontinent, and are keys to illustrating the supercontinent circle. The geological, petrological, geochronological and geochemical data of the newly discovered meta-felsic and meta-mafic magmatic rocks from the Wulonggou area are presented in this study to shed light on the Mesoproterozoic geodynamic setting of the Central Kunlun Belt and the Qaidam Block. Zircon U-Pb geochronological results indicate that the crystallization ages of the meta-felsic samples are 1385–1376 Ma, and the meta-mafic is 1379 ± 25 Ma (MSWD=0.17). Samples from the meta-felsic unit have SiO2 contents of 68.37–73.03 wt% and belong to the high-K calc-alkaline series. They exhibit similar REE distribution patterns and display enrichment in light rare earth elements (LREES) and negative Eu anomalies. Enrichments in Rb, Ba, Th, U and K, depletion in Nb, Ta, Sr, P and Ti are seen in the primitive mantle-normalized trace element pattern diagram. Magmatic zircons from different meta-felsic samples yield variable εHf(t) values of −8.14 to + 9.37 corresponding to ca. 1.7–2.0 Ga two-stage Hf model ages. Samples from the meta-mafic unit have low SiO2 concentrations of 49.87–50.43 wt%, high contents of Fe2O3T, MgO, CaO and TiO2, and Mg# values of 52–58. They show low total REE concentrations of 19.8–30.4 µg/g, and depletion in LREES, flat HREES distribution patterns with (La/Yb)N of 0.27–0.53 and insignificant Eu anomalies. Flat distribution pattern of high field strength elements (HFSEs) is observed in the primitive mantle-normalized trace element pattern diagram. They display similar immobile elements’ concentrations and distribution patterns, low Ti/Y, Nb/Y, La/Yb, and high Nb/La ratios, comparable with the present-day normal middle ocean ridge basalt. Zircons from the meta-mafic sample have mostly positive εHf(t) values ranging from −0.10 to + 4.10 with a single stage Hf model ages of ca. 1.7–2.0 Ga. The geochemical result implies that the meta-felsic unit was generated by partial melting of the Paleoproterozoic juvenile mafic lower-crustal material with mantle attributions, and the meta-mafic unit was probably from partial melting of the lithospheric mantle. Synthesizing the above evidences, Wulonggou Mesoproterozoic meta-magmatic rocks are a bimodal suite formed in a continental extensional tectonic setting which is probably related to the break-up of the Columbia supercontinent.

Mineralogical Characterization and Geochemical Signatures of Supergene Kaolinitic Clay Deposits: Insight of Ropp Complex Kaolins, Northcentral Nigeria

This study presents the chemical and mineralogical composition of clay deposits and associated rock types within the Ropp Complex in order to assess the influence of parent lithology on the kaolinization, genesis, and utility of the deposit. Representative kaolin samples from E horizons of the weathering profiles and their bedrocks were collected from six sites in the Ropp Complex. Clay mineralogy was determined via the XRD technique, while a geochemical analysis was conducted using XRF, SEM coupled with EDS, and ICP-MS. The results showed that all kaolins dominantly contain kaolinite with a content of 77%–98% except for the AS1 kaolin with only minor kaolinite (20%) but mainly illite (65%). The notably lower crystallinity of kaolinite (HI value of 0.53–1.1) as well as its markedly small grain size is consistent with the formation of kaolinite from intensive chemical weathering of igneous rocks. The AS1 kaolin was probably formed from hydrothermal alteration in the burial stage due to the heating of groundwater by the late volcanism. Mobile trace elements (Sr, Ba, and Eu) exhibited a depletion trend, while immobile elements (Hf, Ta, Th) showed enrichment. The relatively more zirconium in kaolins implies the formation of low-temperature kaolinization. The notably high kaolinite content, accompanied by reasonable levels of Fe2O3 and TiO2, signifies a medium-grade quality. Furthermore, chondrite-normalized rare earth element (REE) patterns exhibit congruent trends in rocks and kaolin samples, indicating a relative enrichment in light rare earth elements (LREEs) alongside a discernible negative Eu anomaly. The abundant kaolinite and silicon–aluminum composition make the kaolins suitable for refractories, pharmaceutics, cosmetics, and supplementary cementitious material (SCM).

The Characteristics and Enrichment Process of Dabu Ion-Adsorption Heavy Rare-Earth Element (HREE) Deposits in Jiangxi Province, South China

Ion-adsorption rare-earth deposits supply over 90% of the global market’s heavy rare-earth elements (HREEs). The genesis of these deposits, particularly HREE deposits, has garnered significant attention. To elucidate the metallogenic mechanisms of HREE deposits, a comprehensive study of the weathering profile of granite was conducted in Jiangxi Province, South China. This study focuses on the following two aspects: the petrogeochemistry of HREE-rich granite and the enrichment and fractionation of rare-earth elements (REEs) during the weathering process. The results suggest that the Dabu granites are a typical peraluminous, high-K, calc-alkaline granite series with high silica content (SiO2: 74.5%–76.4%), relatively low phosphorus content (P2O5: &lt;0.05%), and high HREE content (ΣLREE/ΣHREE: 0.16–0.66). Weathering advances the decomposition of minerals and the release of elements. REEs are mainly fixed in the regolith by scavengers, mainly clays, Fe–Mn oxides, and carbonates, and ΣREE can reach 799 ppm in the B horizon. However, HREEs tend to migrate further and preferentially combine with Fe–Mn oxides and carbonates as compared to LREEs, leading to a significant fractionation of REEs in the regolith (ΣLREE/ΣHREE = 0.2–1.1). Additionally, the differential weathering of REE-bearing minerals and the precipitation of secondary REE-bearing minerals are also vital for REE fractionation.

Elemental Geochemistry and Pb Isotopic Compositions of the Thick No. 7 Coal Seam in the Datun Mining Area, China

Thick coal seams recorded abundant petrological, geochemical, and mineralogical information regarding their formation, which in turn can reflect the characteristics of the coal-forming environments, provenance attributes, paleoclimate, and so on. In order to explore the geochemical and lead isotope characteristics of thick coal seams, the No. 7 coal seam in the Datun mining area, Jiangsu Province of China, was selected as the research object. In this work, 29 samples (including coal, roof, and floor rock samples) were collected from three coal mines in the Datun mining area. Through an analysis of the mineral composition and element geochemical characteristics in the coal samples, the enrichment degree of trace elements and modes of rare earth elements were determined. The genetic mechanism of abnormal enrichment of enriched elements is discussed, especially the modes of occurrence and isotope characteristics of Pb. The results showed the following: (1) The main minerals in the coal samples include quartz, potassium feldspar, plagioclase, calcite, dolomite, pyrite, gypsum, and clay minerals, with clay minerals, calcite, quartz, and dolomite being the most common. (2) The major element oxides in coal mainly include SiO2, Al2O3, Fe2O3, MgO, CaO, Na2O, K2O, TiO2, P2O5, and FeO. In the vertical direction, the variation of SiO2, Al2O3, Fe2O3, MgO, K2O, and FeO in coal samples from the three coal mines is consistent. The average value of Al2O3/TiO2 in the samples of Kongzhuang, Longdong, and Yaoqiao coal mines is 28.09–50.52, which basically locates the samples in the felsic source area, such that the sediment source is considered to be felsic source rock. (3) Elements U, La, Pb, and other elements are more enriched in Kongzhuang coal mine samples; elements Th, U, La, Pb, and other elements are more enriched in the Longdong coal mine samples; and elements Th, U, La, Pb, and other elements are more enriched in the Yaoqiao coal mine samples. Furthermore, W is enriched in Yaoqiao mine samples and is highly enriched in Longdong mine samples. The mining area is generally rich in the elements U, La, and Pb. The distribution curves of rare earth elements in the three mines are inclined to the right, with negative Eu anomalies. The enrichment is of the light rare earth enrichment type. (4) Pb isotope data show that the samples from the three mines are mainly distributed in the orogenic belt and the subduction zone lead source areas, where the upper crust and the mantle are mixed, with individual sample points distributed in the mantle and upper crust lead source areas.

Audio magnetotelluric view of the giant carbonatite-hosted Bayan Obo REE deposit, Inner Mongolia, northern China

As critical minerals in low-carbon economies, rare-earth elements (REEs) are crucial for modern industry, technology, and medicine. The largest known REE resource in the world is the Bayan Obo (BO) deposit in northern China. However, BO features as complicated mineral compositions and has experienced several geological events. As a reuslt, controversy remains about the BO REE genesis and enrichment mechanism, and debates are also ongoing about the controlling structure of this giant deposit. We carried out an multiscale electromagnetism study on BO mineral deposits. The multiscale study consists a microscale on samples, a small scale targeting mineral deposits and a mid scale concerning the mine field. The small and mid scale study were conducted using audio-magnetotelluric (AMT). This study revealed the controlling structure using geoelectrical characteristics. AMT data were acquired from more than 590 stations, and the petro-electromagnetism of several samples was analyzed to understand the geoelectrical features of the ore deposits and their surrounding rocks. The data were interpreted using Bostick transformation and generalized least-squares inversions. We obtained the geoelectrical structure of the BO complex down to a maximum depth of 3500 m, and we present two-dimensional imaging based on the AMT conversion results. The results show that the BO deposit developed at the transition of the high- and low-resistivity geoelectrical structure from south to north. Our AMT results indicate that the tectonic setting of the BO deposit is the transition zone between the rift edge and craton margin slope. The ore geology is presently controlled by the complex slope and the rift remnant, the ore-bearing dolostone in the profiles is Y-shaped. It goes downward from south to north and potentially features a great mineral prospect deep in the BO deposit.

Zircon U-Pb geochronology, major, trace elemental, and Sr-Nd-Pb isotopic geochemistry: constraints on the age and magmatic origin of Mesozoic mafic dykes in the Guangxi Zhuang Autonomous Region, South China

ABSTRACT As a direct product of lithospheric extension, the mafic dyke group have become an ideal object for studying the formation, evolution and dynamics of both the crust and continental orogenic belts. Given the scientific significance of mafic dykes and their utility in addressing outstanding questions concerning the origin and development mafic dyke swarms Mesozoic age with-in the South China Plate, in this study, 54 representative mafic dykes within the Guangxi Zhuang Autonomous Region, South China, were examined. Research methods include laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) U-Pb age-dating, whole rock geochemistry, and the Sr-Nd-Pb isotope geochemistry of the studied mafic dykes. The results indicate that these rocks formed between 139 Ma and 113 Ma and have typical doleritic and lamellar textures. They fall into the alkaline and shoshonitic series, are characterized by enrichment of light rare earth elements, some large ion lithophile elements (Rb, Ba, and Sr), Th, U, and Pb, and have depleted Nb, Ta, Hf, and Ti. Moreover, the mafic dykes studied have high initial87Sr/86Sr ratios (0.7055–0.7057), negative εNd(t) values (from −15.2 to −11.4), and relatively constant initial Pb isotopic ratios (that are Enriched Mantle-1 (EM I)-like; 206Pb/204Pb = 16.765–16.816, 207Pb/204Pb = 15.429–15.476, and208Pb/204Pb = 36.882–37.144). The above results indicate that the group of dolerites and lamprophyres studied herein were likely derived from magma generated via low-degree partial melting (1.0%–10%) of an EM1-like garnet-lherzolite mantle source. The parental magmas to these fractionated olivine-, clinopyroxene-, plagioclase, and Ti-bearing phases, with negligible crustal contamination during ascent and dyke emplacement. On the basis of existing research and evidence from this study, we propose a reasonable model for the origin of the mafic dykes: the ancient Pacific Plate subducting below the South China plate led to extension of the lithosphere, an upsurge of the asthenosphere, which triggered partial melting of the lower mantle lithosphere in the Early Cretaceous, and the formation of the parent magma to the Mesozoic mafic dykes in the Guangxi Zhuang Autonomous Region study area. The involvement of slab-derived fluids from the subduction of the ancient Pacific Plate was responsible for metasomatism of the mantle source to these mafic magmas.

Lower Gondwana palaeobotany and geochemistry of phosphorite occurrence in the north‐western part of Ib‐River Coalfield, Odisha, India, and their implications

The present investigation breaks new ground by examining the Raniganj sediments in the Kendudihi section of the Ib‐River Coalfield, Odisha, India. The study identifies a megaflora consisting of 25 species of Glossopteris, Vertebraria indica, stem casts and equisetaceous stems. The microflora is predominantly composed of Striatopodocarpites spp., with a secondary presence of Densipollenites spp. The lithological signatures, including off‐white fine‐grained sandstone with thin bands of silty shale and grey shale, indicate that these sediments belong to the Late Permian succession of the Lower Gondwana sequence, specifically the Raniganj Formation. The macrofloral assemblage found in the lowermost grey shale can be attributed to the Wordian–Capitanian age, while the microfloral assemblage in the upper silty shale resembles that of the Wuchiapingian‐Changhsingian age. Well‐preserved palynomorphs and megafossils, along with the abundant occurrence of lath‐shaped translucent phytoclasts in the grey and silty shale of the Raniganj sediments exposed in the Kendudihi section, explicitly suggest that the sediments were deposited in proximal, low‐energy swampy settings. Additionally, the moderate occurrence of charcoal (20%), along with the existence of degraded organic matter (DOM: 7.6%) and amorphous organic matter (AOM: 16.4%), indicates that the sediments might have been deposited in oxic–dysoxic conditions. The palynological and megafloral studies reveal a warm‐temperate climate with low humidity and intermittent spells of hot and cold seasons, associated with abundant rainfall. The occurrence of phosphorite in the form of nodules and thin lenses, as well as biogenic structures at the juncture of the Raniganj and Barren Measures formations, suggests a marine incursion in the area during the deposition of the late Barren Measures and early Raniganj sediments. X‐ray diffraction (XRD) analysis identified fluorapatite (Ca5(PO4)3F) as the predominant phosphatic mineral phase in the phosphatic nodule, siltstone and claystone. The Post‐Archean Australian Shale composition, normalized rare earth element (REE) patterns of samples from this area, reveals slight positive La (average La anomaly: 1.02) and Gd (average Gd anomaly: 1.05) anomalies and heavy REE enrichment compared to light REE, explicitly indicating a marine environment.

Multi-stage evolution of the monzonitic Larvik Plutonic Complex (Oslo Rift, Norway) and its implications for the formation of the Kodal Fe-Ti-P(−REE) deposit

The Larvik Plutonic Complex is a monzonitic complex that was emplaced early during the formation of the Permian Oslo Rift (southern Norway). It extends across its entire width (around 50 km), and is made up of a majority of larvikite (augite monzonite) and lardalite (nepheline monzogabbro to nepheline syenite) distributed in ten successive intrusive units that partially intersect each other. The Larvik Plutonic Complex also hosts occurrences of singular Fe-Ti-P-rich rocks of magmatic origin, including the Kodal deposit. These are mainly composed of titanomagnetite, ilmenite, titanaugite and apatite, the latter also featuring rare earth elements (REE) enrichment. Here, we aim to unravel the conditions that allowed the Kodal deposit to form, and determine why other mineralized bodies are not seen elsewhere in the Larvik Plutonic Complex. We compared the petrography and elemental and isotope (Sr, Nd and Hf) geochemistry of both the Kodal mineralization and the neighboring larvikite, in order to provide evidence of their petrogenetic relationship. Both lithologies share the same isotopic ratios (87Sr/86Sr(i): 0.7035–0.7043; εNd(i): +2.37 − +3.48; εHf(i): +3.39 − +9.16), which would suggest a single homogeneous source. The very low dispersion of our isotopic data also suggests that crustal contamination levels in the area were low to negligible. Normalized trace diagrams of larvikite in several localities of the Larvik Plutonic Complex also show enrichments in most incompatible elements, which becomes more prevalent towards the Kodal deposit. Elements like Sr and Eu(2+) follow an opposite trend, because of their compatibility in plagioclase. We therefore infer that the region around the Kodal deposit hosts more fractionated larvikite due to the previous crystallization of successive plagioclase cumulates. We deduce that the Kodal lobe corresponds to a more evolved intrusion, which is no part of Pluton V per se, as considered in the literature until now, but instead derives at least from a monzonitic magma at the origin of the plutons V to VIII). This also implies that the formation of Fe-Ti-P mineralization at Kodal was most likely a consequence of enrichment of the residual melt in alkaline elements and incompatible elements. These conditions support an early hypothesis of formation by silicate-liquid immiscibility, along with petrographic evidence of disequilibrium at the mineralogical scale. However, further analyses would be required to test the hypotheses of silicate-liquid immiscibility against an accumulation of the Fe-Ti-P mineralization from an evolved intermediate magma.

Plagioclase Megacrysts in Mesoproterozoic Amphibolites from the New Jersey Highlands, USA: Indicators of Mixed-Source Magma and Fractionation Interruption in Anorthosite-Dominated Terrains

Rare amphibolite in the New Jersey Highlands containing plagioclase megacrysts ≤13 cm long forms bodies 0.5 to 2 m thick that preserve a penetrative metamorphic fabric and have sharp, conformable contacts against Mesoproterozoic country rocks. The megacrystic amphibolites were emplaced as thin dikes along extensional faults between 1160 and 1130 Ma. Amphibolites contain weakly zoned, subhedral andesine megacrysts (An29–44) in a matrix of plagioclase (An18–38), magnesio-hastingsite, biotite, diopside, Fe-Ti oxides, and apatite. The whole-rock major oxide composition of the megacrystic amphibolite matrix has high TiO2 (2.07 wt.% ± 2.0%), Al2O3 (17.03 wt.% ± 0.87%), and Fe2O3t (12.84 wt.% ± 3.2%) that represents an Al-Fe-rich mafic magma type that is characteristic of anorthosite associations globally. The whole-rock, rare earth element (REE) composition of the megacrystic amphibolite matrix is characterized by enrichments in light rare earth elements (LREEs) (La/YbN = 1.73–10.69) relative to middle (MREEs) and heavy (HREEs) rare earth elements (Gd/YbN = 1.30–1.85), and most samples have small positive Eu anomalies (Eu/Eu* = 0.95–1.25). The megacrystic amphibolite matrix is also enriched in large ion lithophile elements (LILEs) and depleted in high field strength elements (HFSEs) (e.g., Ba/Nb = 24–22). Megacrystic amphibolites formed through partial melting of subduction-modified lithospheric mantle that fractionated olivine and plagioclase, producing a high-Al-Fe mafic magma. Plagioclase megacrysts formed through extraction of a plagioclase-rich crystal-liquid mush from anorthosite that mixed with mafic magma and collected in the upper part of the mid-crustal magma (depth of ~20 km based on Al-in-hornblende geobarometry) chamber through flotation. Periodic tapping of this mixed source by extensional fractures led to emplacement of the amphibolites as dikes and may have interrupted the extensive fractionation and plagioclase separation necessary to form voluminous anorthosite intrusions.

Slab break-off of the Kalamaili oceanic slab revealed by the latest Carboniferous mafic–ultramafic rocks in eastern North Tianshan (NW China)

Identifying the tectonic transition from oceanic subduction to collision is crucial for tracking the final stage evolution of ancient orogenic belts. In this study, we present new geochronological and geochemical data for the Mozbaysay mafic–ultramafic complex in the Balikun area, eastern North Tianshan of the southern Central Asian Orogenic Belt. This complex had intruded into the late Carboniferous volcano-sedimentary rocks and is comprised mainly of hornblende gabbro and lherzolite. Zircon U-Pb ages of the hornblende-gabbros reveal that this complex was emplaced at ca. 305 Ma. Geochemical analyses suggest these mafic–ultramafic rocks are characterized by slight enrichment of light rare earth elements (LREEs) and relatively depleted heavy rare earth elements (HREEs), resembling enriched mid-ocean ridge basalt (E-MORB). They also exhibit restricted (87Sr/86Sr)i ratios (0.702396–0.704295) and εNd(t) values (+7.0 to +9.1), indicative of a depleted mantle source with minimal crustal contamination. Incompatible element ratios (i.e., Nb/Ta, Zr/Hf, Rb/Nb, and Ba/Nb) suggest the involvement of subducted slab-derived aqueous fluids in their mantle source. These collectively indicate that the parental magmas of the Mozbaysay mafic–ultramafic rocks may have been generated by a mixed mantle source consisting of the E-MORB-like asthenospheric mantle, subcontinental lithospheric mantle (SCLM), and hydrous fluids from subducted slab. Furthermore, a slab break-off model is proposed to explain the generation of these latest Carboniferous mafic–ultramafic rocks. Integrating these findings with regional geological data, we propose that the tectonic transition from subduction (slab roll-back) to collision (slab break-off) along the Kalamaili suture zone occurred at ca. 305–300 Ma.

Anthropogenic impact of rare earth elements on groundwater and surface water in the watershed of the largest freshwater lake in China

Limited knowledge exists regarding the potential risks associated with anthropogenic release of rare earth elements (REEs) in the environment. This study aimed to investigate REE signatures in the watershed Poyang Lake, the largest freshwater lake in China. Samples of surface water, wastewater, and groundwater were collected from five rivers discharging into the lake. Results revealed wastewater from wastewater treatment plants contained total REE concentrations from 231 to 904 μg/L, exceeding those found in surface water (0.4 to 1.3 μg/L) and groundwater (0.5 to 416 μg/L). Samples with elevated REE were found in Ca-Mg-Cl/SO4 type waters and exhibited an 18OD deviation from local meteoric water line. Wastewater exhibited a higher positive Gd anomaly compared to surface water and groundwater, attributed to anthropogenic input of Gd (Gdanth). The determined Gdanth concentration ranged from 0.04 to 0.21 μg/L, and from 0.06 to 0.37 μg/L, accounting for 4 % to 21 % and 49 % to 84 % of total Gd concentrations in groundwater and surface water, respectively. Gdanth concentration in wastewater (0.19 to 0.43 μg/L) remained constant in effluent after wastewater treatment. Surface water displayed relatively complex normalized REE patterns influenced by anthropogenic activities and natural processes (weathering and complexation), while groundwater exhibited heavy REEs enrichment, due to carbonate solution complexation. Additionally, Gdanth concentration showed a positive correlation with ΣREE, Pb, Ni, and Co concentrations in groundwater, indicating a good pollution tracing potential. Health risk assessment using the hazard quotient (HQ) suggested higher HQGd values in groundwater compared to surface water. Residents in the eastern part of Poyang Lake were found to face higher risks associated with Gd in groundwater compared to the western part, with infants and children at greater risk than adult males and females. These findings offer valuable insights into environmental behavior and health risks of REEs in aquatic systems impacted by human activities.